Removable color layer for artificial nail coatings and methods therefore

ABSTRACT

The present disclosure relates to a nail coating system comprising a basecoat, a color layer, and a topcoat. The system of the present disclosure may be applied to natural and/or pre-existing artificial nail coatings. The present disclosure relates generally to compositions for natural and artificial nail coatings, and particularly, but not by way of limitation, to polymerizable compositions and color layers polymerized therefrom. The disclosure further relates to methods of making a polymerized color layer.

RELATED APPLICATION

This application is a continuation of U.S. application Ser. No.12/573,633 filed Oct. 5, 2009 the content of which is incorporatedherein by reference in its entirety.

FIELD OF THE INVENTION

The present disclosure relates generally to compositions for nailcoatings, and particularly, but not by way of limitation, topolymerizable compositions and color layers polymerized therefrom.

BACKGROUND

The information provided below is not admitted to be prior art to thepresent invention, but is provided solely to assist the understanding ofthe reader.

Artificial fingernail and toenail compositions in the form of nailcoatings and extenders are well known and have become a major productline in the appearance and beauty industry. The appearance of one'sfingernails (and in many cases also toenails) has become of importanceto many fashion conscious individuals. Commercial artificial nailcompositions have been used to enhance the appearance of natural nailsand also to enhance the physical properties of natural nails, includingstrengthening fragile nail surfaces.

Conventional natural nail coatings may be classified into twocategories: nail polishes; also known as lacquers, varnish or enamelsand artificial nails; also known as gels or acrylics. Nail polishestypically comprise various solid components which are dissolved and/orsuspended in non-reactive solvents. Upon application and drying, thesolids deposit on the nail surface as a clear, translucent or coloredfilm. Typically, nail polishes are easily scratched and are easilyremovable with solvent, usually within one minute and if not removed asdescribed, will chip or peel from the natural nail in one to five days.

Conventional artificial nails are comprised of chemically reactivemonomers, and/or oligomers, in combination with reactive or non-reactivepolymers to create systems which are typically 100% solids and do notrequire non-reactive solvents. Upon pre-mixing and subsequentapplication to the nail plate, or application and exposure to UVradiation, a chemical reaction ensues resulting in the formation of along lasting, highly durable cross-linked thermoset nail coating that isdifficult to remove. Artificial nails may possess greatly enhancedadhesion, durability, as well as scratch and solvent resistance whencompared to nail polishes. However, because of these inherentproperties, such thermosets are much harder to remove, should theconsumer so desire. Removal typically requires soaking in non-reactivesolvents for 30-90 minutes (for acrylics and currently available“soakable gels”; it may take more than 90 minutes to remove traditionalUV nail gels by solvent) and typically may also require heavily abradingthe surface of the artificial coating or scrapping with a wooden ormetal probe to assist the removal process.

There remains a need for a cosmetic product that possesses the enhancedadhesion properties of thermosets and also possesses the ease of removalmore similar to that of polishes.

The present disclosure forms part of a nail coating system comprising areactive basecoat adhesion layer (Application Ser. No. 12/555,571 (US2011/0060065), the present disclosure, an intermediate, decorative andreactive color layer (Application Ser. No. 12/573,633, US 2011/0081306),and a protective and reactive topcoat (Application Ser. No. 12/573,640,US 2011/0082228). The contents of each application are mutuallyincorporated into each of the others by reference for all purposes.

Other objects and advantages will become apparent from the followingdisclosure.

SUMMARY OF INVENTION

Aspects of the present disclosure when taken in conjunction with therelated disclosures provide a basecoat characterized by firm adhesion toa nail surface combined with a solvent-induced “unzipping,”“quick-release” feature that affords facile removal. Aspects of thepresent disclosure when taken in conjunction with the relateddisclosures provide a color layer characterized by firm adhesion topolymer surfaces combined with a solvent-induced “unzipping,”“quick-release” feature that affords facile removal. Further aspects ofthe present disclosure when taken in conjunction with the relateddisclosures provide a protective topcoat characterized by firm adhesionto polymer surfaces combined with a solvent-induced “unzipping,”“quick-release” feature that affords facile removal.

An aspect of the present disclosure provides a nail coating comprising a3-dimentional (3-D) thermoset lattice interpenetrated by a networkcomprising an organic solvent-dissolvable resin. According to an aspectof the disclosure, the 3-D thermoset lattice provides the enhancedadhesion, toughness, and scratch-resistance of conventional artificialnails. According to an aspect of the disclosure, an interconnectedsystem of voids and an interpenetrating network of an organicsolvent-dissolvable resin provides the ease of solvent removability.

According to an aspect, the present disclosure provides a liquidcomposition comprising at least one monomer, and/or oligomer, and/orpolymer which polymerize to a 3-D thermoset. According to an aspect, thepresent disclosure provides a liquid composition comprising at least oneorganic solvent-dissolvable resin. According to an aspect, the organicsolvent-dissolvable resin forms a network of inclusions within the 3-Dthermoset lattice.

According to an aspect, the present disclosure provides a viscous liquidcomposition comprised of one or more addition-polymerizable,ethylenically-unsaturated monomers.

According to an aspect, the present disclosure provides a monomer whichconfers the “unzipping” property of ease of removal of the polymerizedlattice. According to an aspect, the monomer may be polypropyleneglycol-4-monomethacrylate (PPG4 monomethacrylate). According to anaspect, suitable monomers may include any acrylated or methacrylatedmonomer in the polyethylene glycol (PEG) or polyopropylene glycol (PPG)families. According to an aspect, the “unzipping” monomers are presentat from about 0 to about 70 weight % (wt %).

According to an aspect, the liquid composition comprises reactivemonomers, and/or oligomers, and/or polymers which provides thepolymerized composition increased adhesion. According to an aspect, suchreactive monomers, and/or oligomers, and/or polymers may be a(meth)acrylate. As is known to persons of skill in the polymer arts, theterm (meth)acrylate encompasses acrylates and/or methacrylates.

According to an aspect, such reactive monomers, and/or oligomers, and/orpolymers may be selected from the group consisting ofhydroxyethylmethacrylate (HEMA), hydroxypropylmethacrylate (HPMA), ethylmethacrylate (EMA), tetrahydrofurfuryl methacrylate(THFMA), pyromelliticdianhydride di(meth)acrylate, pyromellitic dianhydride glyceryldimethacrylate, pyromellitic dimethacrylate, methacroyloxyethyl maleate,2-hydroxyethyl methacrylate/succinate,1,3-glyceroldimethacrylate/succinate adduct, phthalic acid monoethyl methacrylate,acetoacetoxy ethyl methacylate (AAEMA), and mixtures thereof. Accordingto an aspect, such reactive monomers, and/or oligomers, and/or polymersmay possess acidic functionality. According to an aspect, the monomer,oligomer or polymer which provides the polymerized composition increasedadhesiveness is present from about 0 to about 50 wt %.

An aspect of the present disclosure provides a polymerizable liquidcomposition comprising a non-reactive, solvent-dissolvable polymer.According to an aspect, the non-reactive, solvent-dissolvable polymer isa cellulose ester. According to a particular aspect, the non-reactive,solvent-dissolvable polymer is a cellulose acetate alkylate. Accordingto a more particular aspect, the non-reactive, solvent-dissolvablepolymer is a cellulose acetate butyrate or a cellulose acetatepropionate. According to a further aspect, the ingredient which providesfor ease of removal may be present at from about 0.1 to about 75 wt %.

According to an aspect of the disclosure, the color layer compositionmay comprise up to 10 wt % of pigments and/or dyes.

An aspect of the present disclosure provides methods of removal.According to an aspect, the thermoset polymerized from the disclosedcomposition is provided an increased sensitivity to organic solventsand, in particular, to acetone. According to an aspect of thedisclosure, means are provided to distribute organic solvent to thepolymer/natural nail interface. According to an aspect, delivering anappropriate solvent to the polymer/natural nail interface will result inan unzipping effect which leads to rapid disruption of the adhesive bondinterface and greatly facilitates quick and gentle removal from thenatural nail.

Still other aspects and advantages of the present invention will becomereadily apparent by those skilled in the art from the following detaileddescription, wherein it is shown and described preferred embodiments ofthe invention, simply by way of illustration of the best modecontemplated of carrying out the invention. As will be realized, theinvention is capable of other and different embodiments, and its severaldetails are capable of modifications in various obvious respects,without departing from the invention. Accordingly, the description is tobe regarded as illustrative in nature and not as restrictive.

BRIEF DESCRIPTION OF DRAWINGS

Not Applicable.

DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT

Nail coatings commonly consist of a material applied to a keratin nailsurface. Prior art coatings may damage the nail by at least twomechanisms. First, adequate adhesion of the enhancement to the naturalnail may require abrasion to roughen the nail surface. And second,removal of the enhancement may require prolonged exposure to possiblydamaging solvents and or further abrasion of the artificial nailsurface.

An embodiment of the present disclosure provides a nail coatingcomprising a 3-dimentional (3-D) thermoset lattice interpenetrated by anetwork comprising an organic solvent-dissolvable resin. According to anaspect of the disclosure, a 3-D thermoset lattice provides the enhancedadhesion, toughness, and scratch-resistance of conventional artificialnails. According to an embodiment, a basecoat is interposed between thenatural nail surface and the present color layer.

The terms “nail” and “nail surface” mean the natural, keratinous nailsurface, or a natural nail to which a pre-formed artificial nail or nailtip is adhered. In other words, the polymerizable compositions of theinvention may be applied directly to the keratinous surface of thenatural nail, or to a nail surface having affixed thereto a pre-formedartificial nail or nail tip enhancement.

The invention comprises a polymerizable composition for application tothe nails and polymerization thereon to yield an artificial nailstructure. The polymerizable composition is preferably an anhydrousliquid, having the consistency of a semi-mobile gel to freely mobileliquid at room temperature. Immediately prior to use, the polymerizablecomposition is applied to the nail surface and shaped by the nailtechnician. After polymerization an artificial nail structure isobtained.

An embodiment of the liquid composition comprises reactive monomers,and/or oligomers, and/or polymers which provides the polymerizedcomposition increased adhesion. In certain embodiments, such reactivemonomers, and/or oligomers, and/or polymers may be a (meth)acrylate. Asis known to persons of skill in the polymer arts, the term(meth)acrylate encompasses acrylates and/or methacrylates. According toan aspect, such reactive monomers, and/or oligomers, and/or polymers maybe selected from the group consisting of hydroxypropyl methacrylate(HPMA), hydroxyethyl methacrylate (HEMA), EMA, THFMA, pyromelliticdianhydride di(meth)acrylate, pyromellitic dianhydride glyceryldimethacrylate, pyromellitic dimethacrylate, methacroyloxyethyl maleate,2-hydroxyethyl methacrylate/succinate,1,3-glyceroldimethacrylate/succinate adduct, phthalic acid monoethyl methacrylate,acetoacetoxy ethyl methacrylate (AAEMA), and mixtures thereof. Accordingto an aspect, such reactive monomers, and/or oligomers, and/or polymersmay possess acidic functionality. According to an aspect, the monomer,oligomer or polymer which provides the polymerized composition increasedadhesiveness is present from about 0 to about 50 wt %.

The ethylenically unsaturated reactant may be mono-, di-, tri-, orpoly-functional as regards the addition-polymerizable ethylenic bonds. Avariety of ethylenically unsaturated reactants are suitable, so long asthe reactants are capable of polymerization to yield a polymerizedartificial nail structure upon exposure to the appropriate stimuli.Suitable ethylenically unsaturated reactants are disclosed in U.S. Pat.No. 6,818,207 which is incorporated by reference.

Certain embodiments of the liquid composition comprise at least onemonomer which confers the “unzipping” property by imparting to theinterfacial bonds a sensitivity to organic solvent. According to anaspect, the at least one monomer may be polypropyleneglycol-4-monomethacrylate (PPG4 monomethacrylate). According to anaspect, suitable monomers may include any acrylated or methacrylatedmonomer in the PPG or polyethylene glycol (PEG) family. According to anaspect, the “unzipping” monomers are present at from about 0 to about 70weight % (wt %).

An embodiment of the present disclosure provides a polymerizable liquidcomposition comprising a methacrylate monomer which provides improvedadhesion, viscosity, wear and durability. In certain embodiments, themethacrylate monomer is a tetrahydrofurfural methacrylate. In otherembodiments, some or all of the tetrahydrofurfural methacrylate may besubstituted by such monomers including, but not limited to ethylmethacrylate (EMA), HPMA, and other monomers such as pyromelliticdianhydride glyceryl dimethacrylate, and similar (meth)acrylatemonomers. The methacrylate monomer may be present from about 0 to about70 wt %.

Certain embodiments of the polymerizable liquid composition of thepresent disclosure may comprise a urethane (meth)acrylate resin whichmay convey flexibility and toughness to the polymerized product. Incertain embodiments, urethane methacrylates are preferred. The urethane(meth)acrylate monomer may be present from about 0 to about 50 wt %. Incertain embodiments, the urethane (meth)acrylate may have a molecularweight (grams/mole) of from about 100 to about 20,000. In certainembodiments, the urethane (meth)acrylate may have a molecular weight offrom about 300 to about 15,000. In certain embodiments, the urethane(meth)acrylate may have a molecular weight of from about 500 to about13,000. In certain embodiments, the urethane (meth)acrylate may have amolecular weight of from about 500 to about 6,000.

In certain embodiments of the disclosure, the 3-D thermoset lattice isinterpenetrated by a network of voids left by the evolution of anon-reactive solvent. During the curing process, domains of anon-reactive, organic solvent-dissolvable resin form within thecrosslinked polymer matrix. When it is desired to remove the nailcovering, the polymer is exposed to a solvent which penetrates thenetwork of voids to the domains of the solvent-dissolvable resin.Dissolution of the resin allows further penetration of solvent to theinterior of the thermoset and also to the basecoat/color layerinterface.

Certain embodiments of the polymerizable liquid composition of thepresent disclosure may comprise a non-reactive, solvent-dissolvablepolymer. According to an aspect, the non-reactive, solvent-dissolvablepolymer is a cellulose ester. According to a particular aspect, thenon-reactive, solvent-dissolvable polymer is a cellulose acetatealkylate. According to a more particular aspect, the non-reactive,solvent-dissolvable polymer is a cellulose acetate butyrate or acellulose acetate propionate. The non-reactive, solvent-dissolvablepolymer may be a mixture of any acceptable non-reactive,solvent-dissolvable polymer. According to a further aspect, thenon-reactive, solvent-dissolvable polymer may be present at from about0.1 to about 75 wt %.

According to certain embodiments, the color layer further comprises atleast one rheology modifying agent. In certain embodiments, the rheologymodifier is present at up to 10 wt %. In certain embodiments therheology agent may be present to provide a thixotropic property to thecomposition to aid in the suspension of pigment particles. In certainembodiments, the rheology agent may be a fumed silica. In certainembodiments, the rheology agent may be a polyamide.

The compositions of the invention may contain from about 0.001-5% byweight of a plasticizer. The plasticizer causes the polymerized nailstructure to have improved flexibility and reduced brittleness. Suitableplasticizers may be esters, low volatility solvents, or non-ionicmaterials such as nonionic organic surfactants or silicones.

Suitable esters include those having the general structure RCO—OR′ whereRCO—represents a carboxylic acid radical and where—OR' is an alcoholresidue. Preferably R and R′ are fatty radicals, having 6 to 30 carbonatoms, and may be saturated or unsaturated. Examples of suitable estersare those set forth on pages 1558 to 1564 of the C.T.F.A. CosmeticIngredient Dictionary and Handbook, Seventh Edition, 1997, which ishereby incorporated by reference. In the preferred compositions of theinvention, the plasticizer is an ester of the formula RCO—OR′ wherein Rand R′ are each independently a straight or branched chain C₆₋₃₀ alkyl.A suitable plasticizer is isostearyl isononanoate. Other suitableplasticizers are disclosed in U.S. Pat. No. 6,818,207 which isincorporated by reference.

According to certain embodiments, the color layer further comprises atleast one UV stabilizing agent. In certain embodiments, the UVstabilizer is present at up to 2 wt %.

The compositions of the invention may contain one or more U.V.absorbers, which assist in reducing the yellowing which is often seen inartificial nails. U.V. absorbers have the ability to convert incidentU.V. radiation into less damaging infrared radiation (heat), or visiblelight. A recommended amount of U.V. absorber is 0.001-5% by weight ofthe total composition. Suitable U.V. absorbers include hydroxybenzotriazole compounds and benzophenone compounds such as are disclosedin U.S. Pat. No. 6,818,207, incorporated by reference.

It may be desirable to include one or more polymerization regulators. Apolymerization regulator assists in preventing the polymerization of themonomer composition from occurring too quickly. Hydroquinone and similarmaterials are suitable polymerization regulators. Suggested ranges ofpolymerization regulators are from about 0.0001-5% by weight of thetotal composition. Suitable polymerization regulators are disclosed inU.S. Pat. No. 6,818,207, incorporated by reference.

Without being bound by theory, the present inventors eases removal ofthe nail covering by facilitating entrance of solvent into the interiorof the coating. Conventional polymerized nail coatings are weakened bysurface abrasion followed by long-term (30 to 90 minute) exposure toorganic solvents. The solvent slowly seeps in at the outer surface andedges of the thermoset and eventually swells the coating. The swellingeventually weakens the entire matrix structure, as well as disruptsadhesion to the nail surface. Even a weakly attached nail coating mayrequire abrasion to enhance solvent penetration and speed removal.However, the slow rate at which solvent diffuses through the thermoset,limits the rate of swelling.

The present invention provides a 3-D thermoset interpenetrated by anetwork of solvent-dissolvable channels and inclusions. Upon exposure toorganic solvent, the cellulose ester, or other non-reactive, organicsolvent-soluble polymer, is dissolved and leached from the coating. Theresult is a series of solvent accessible passageways riddled throughoutthe thermoset. Under these conditions, solvent may attack the interiorof the thermoset no longer limited by a slow diffusion rate.

Certain embodiments of the disclosed polymerizable composition may beviscous gels or liquids. Gel or liquid embodiments may be polymerized byexposure to radiant energy, such as heat, visible, U.V., orelectron-beam radiation. Liquid or gel embodiments are applied uponnails and may be shaped to the desired configuration. The coated nailsare exposed to radiant energy, and polymerization occurs.

The inventive composition may be polymerizable with actinic radiation.The actinic radiation may be visible, ultraviolet (UV), or electron beamradiation. The UV radiation may be characterized by a wavelength, orgroup of wavelengths, typically, but not limited to about 320 to about420 nanometers.

After the liquid composition is applied to a surface, especially abasecoat surface, the liquid is cured. The liquid composition comprisesethylenic unsaturated (meth)acrylates which and may be cured by aUV-initiated, free-radical polymerization method. Persons of skill inthe polymerization arts may readily determine suitable photoinitiatorsfor use with the invention. Set forth below are non-limitingrepresentative photoinitiators that are suitable for purposes of theinvention.

A non-limiting suitable photoinitiator is a2,4,6-trimethylbenzoyldiphenylphosphorous derivative. A suitablederivative is ethyl-2,4,6-trimethylbenzoyldiphenylphosphinate, which maybe obtained under the tradename Lucirin® TPO-L (BASF Aktiengesellschaft,Ludwigshafen, DE). Another non-limiting suitable derivative is2,4,6-Trimethylbenzoyldiphenylphosphine oxide, which may be obtainedunder the trade name Lucerin® (BASF) or as Genocure® TPO (Rahn)The2,4,6-trimethylbenzoyldiphenylphosphinate photoinitiator may be presentfrom about 0% to about 20 wt %.

A non-limiting suitable photoinitiator is hydroxycyclohexyl phenylketone, which may be obtained under the tradename Igracure® 184 andwhich may be present from about 0 to about 20 wt %.

A non-limiting suitable photoinitiator is benzil dimethyl ketal (BDK),which may be obtained under the tradename FIRSTCURE® BDK (Albemarle,Baton Rouge, La., US) and which may be present from about 0 to about 20wt %.

Certain embodiments of the disclosed color layer may comprise up to 10wt % pigments and/or dyes. Embodiments of the related basecoat andtopcoat disclosures may have up to 1 wt % pigments and or dyes. Highconcentrations of pigments and/or dyes may absorb UV radiation. Tocompensate therefore, certain embodiments of the present disclosure maycomprise higher concentrations, up to 20 wt %. photoinitiator.

A conventional thermoset nail coating comprises 100% solids and does notcomprise nonreactive solvent. The polymerizable liquid composition ofthe present disclosure further comprises at least one non-reactivesolvent. A suitable non-reactive solvent is readily volatile at roomtemperature and is a good solvent for the remaining ingredients. Uponapplication, the non-reactive solvent readily volatilizes leavingregions of increased porosity. These porous regions later facilitate theentry of a remover solvent which may be acetone.

Suitable non-reactive solvents include, but are not limited to ketones,alkyl acetates, alcohols, alkanes, alkenes, and mixtures thereof.Suitable non-reactive solvents may be selected from the group consistingof acetone, ethyl acetate, butyl acetate, isopropyl alcohol, ethanol,methyl ethyl ketone, toluene, hexane, and mixtures thereof. Aparticularly suitable non-reactive solvent is acetone. Typically anon-reactive solvent or a mixture of non-reactive solvents is includedat up to about 70 weight percent.

Certain embodiments of the formulation may optionally comprise(meth)acrylate monomers and/or polymers in order to fine tune adhesionand removal properties. Non-limiting examples of such (meth)acrylatesinclude: mono or poly(meth)acrylates, HPMA, HEMA, pyromelliticdianhydride di(meth)acrylate, pyromellitic dianhydride glyceryldimethacrylate, pyromellitic dimethacrylate, methacroyloxyethyl maleate,2-hydroxyethyl methacrylate/succinate, 1,3-glyceroldimethacrylate/succinate adduct, phthalic acid monoethyl methacrylate ,ethyl methacrylate, tetrahydrofurfuryl methacrylate, butyl methacrylate,isobutyl methacrylate, PEG-4 dimethacrylate, PPG monomethacrylate,trimethylolpropane trimethacrylate, hydoxyethyl methacrylate,isopropylidenediphenyl bisglycidyl methacrylate, lauryl methacrylate,cyclohexyl methacrylate, hexyl methacrylate, urethane methacrylate,hydroxypropyl methacrylate, triethylene glycol dimethacrylate, ethyleneglycol dimethacrylate, tetraethylene glycol dimethacrylate,trimethylolpropane trimethacrylate, neopentylglycol dimethacylate,acetoacetoxy ethyl methacylate (AAEMA), and mixtures thereof.

Certain embodiments of the formulation may optionally comprise resins,such as, but not limited to polyvinylbutyral and/or tosylamideformaldehyde resins. Such resins may also act as film formers, adhesionpromoters, and aids to removal. These resins may also qualify assolvent-dissolvable resins which can be extracted to create channels forsolvent absorption and migration.

Certain embodiments of the formulation may optionally compriseplasticizers, such as, but not limited to diisobutyl adipate.Plasticizers act to minimize the effects of brittleness of thesubsequently formed polymer after exposure to UV sun light and air.Plasticizers also are found to slightly shorten the removal time.Plasticizers may be present at from 0 to about 25 wt %. Persons of skillin the polymer arts will appreciate that inclusion of plasticizers abovea certain limit is undesirable because they may impare the integrity anddurability of the coatings.

The unpolymerized color layer may have the consistency of a liquid orgel. The unpolymerized color layer may be applied to an polymerizedbasecoat surface. In an embodiment the polymerized basecoat may be anembodiment of co-pending U.S. application Ser. No. 12/555,571 (US2011/0060065). The polymerized basecoat may be applied to a nail surfaceand contacted with a color layer. The nail surface-basecoat-color layersystem may be exposed to UV radiation. The basecoat and color layer maybe polymerized thereby adhering the color layer to the nail surface.

In an embodiment, a color layer may be removed from the natural nailsurface without abrading the artificial nail surface.

As compared to conventional nail coatings, the present disclosurerelates to a major advantage in that it enables the durable color layerto adhere to the natural nail for periods in excess of two weeks withoutbreakdown of the coating. In contrast to conventional coatings, thepresent disclosure relates to a UV gel system that is non-damaging tothe natural nail. The application process requires no abrasive treatmentof the natural nail. And the process of removal at most calls for theuse of a light touch of a wooden stick. Moreover, in comparison toconventional systems, the present disclosure relates to a more rapidlyremovable nail coating system achieving removal in 20 seconds forbasecoat alone to 20 minutes for the whole system.

The polymerized basecoat of the present invention may adhere to thekeratin nail surface by means of hydrogen bonds. The basecoat and colorlayer may be removed from the nail surface by means of organic solvents.Non-limiting solvents include acetone, butyl acetate, isopropyl alcohol,ethanol, ethyl acetate, methyl ethyl ketone, and mixtures thereof.

Another Ethylenically Unsaturated Monomer

The polymerizable composition preferably contains 5-98%, preferably10-96%, more preferably 25-95% by weight of the total composition of atleast one other ethylenically unsaturated monomer. The ethylenicallyunsaturated monomer may be mono-, di-, tri-, or polyfunctional asregards the addition-polymerizable ethylenic bonds. A variety ofethylenically unsaturated monomers are suitable, so long as the monomersselected are capable of polymerization directly on the nail surface toyield a polymerized artificial nail structure upon exposure to theappropriate stimuli.

Examples of suitable monofunctional ethylenically unsaturated monomersinclude those of the formula: I.

wherein R₁ is H, a.C₁₋₃₀ straight or branched chain alkyl, aryl,aralkyl; R₂ is a pyrrolidone, or a substituted or unsubstitutedaromatic, alicyclic, or bicyclic ring where the substitutents are C₁₋₃₀straight or branched chain alkyl, or COOM wherein M is H, a C₁₋₃₀straight or branched chain alkyl, pyrrolidone, or a substituted orunsubstituted aromatic, alicylic, or bicyclic ring where thesubstitutents are C₁₋₃₀ straight or branched chain alkyl which may besubstituted with one or more hydroxyl groups, or [(CH₂)_(m)O]_(n) Hwherein m is 1-20, and n is 1-200.

Preferably, the monofunctional ethylenically unsaturated monomer is ofFormula I, above, wherein R₁ is H or a C₁₋₃₀ alkyl, and R₂ is COOMwherein M is a C₁₋₃₀ straight or branched chain alkyl which may besubstituted with one or more hydroxy groups.

More preferably, R₁ is H or CH₃, and R₂ is COOM wherein M is a C₁-10straight or branched chain alkyl which may be substituted with one ormore hydroxy groups. In the preferred embodiment of the invention, themonofunctional ethylenically unsaturated monomer is a mixture ofmonomers of Formula I where in one monomer R₁ is H or CH₃ and R₂ is COOMwhere M is a C₁₋₁₀ alkyl, and where in the second monomer R₁ is H orCH₃, and R₂ is COOM where M is a C₁₋₁₀ alkyl substituted with one ormore hydroxy groups.

In the preferred embodiment of the invention, the monofunctionalethylenically unsaturated monomer comprises a mixture of one or moremethacrylate monomers and one or more hydroxyalkyl methacrylatemonomers, preferably about 50-98.5% of a methacrylate monomer, and 5-20%of a hydroxyalkyl methacrylate monomer. Most preferred is a compositioncontaining 60-98.5% ethyl methacrylate and 7-15%hydroxypropylmethacrylate.

Di-, tri- and polyfunctional monomers, as well as oligomers, of theabove monofunctional monomers may also be used in the composition. Suchdi-, tri-, and polyfunctional monomers are generally known ascross-linking monomers because they aid in cross-linking of the monomercomposition during and after polymerization. Preferred difunctionalmonomers include those having the general formula:

wherein R₃ and R₄ are each independently H, a C₁₋₃₀ straight or branchedchain alkyl, aryl, or aralkyl; and X is [(CH₂)_(x)O_(y)]_(z) wherein xis 1-20, and y is 1-20, and z is 1-100. Particularly preferred aredifunctional acrylates and methacrylates, such as the compound offormula II above wherein R₃ and R₄ are CH₃ and X is [(CH₂)_(x)O_(y)]_(z)wherein x is 1-4; and y is 1-6; and z is 1-10.

Particularly preferred are difunctional acrylates and methacrylates,such as the compound of formula II above wherein R₃ and R₄ are CH₃ and Xis [(CH₂)_(x)O_(y)]_(z) wherein x is 2; and y is 1, and z is 4. Thepolymerizable compositions preferably contain 0.1-25%, preferably0.5-20%, more preferably 1-15% by weight of a difunctional monomer.Particularly preferred is where the difunctional monomer is an ethyleneglycol dimethacrylate. Most preferred is where the difunctional monomeris tetraethylene glycol dimethacrylate.

Trifunctional and polyfunctional monomers are also suitable for use inthe polymerizable monomer compositions of the invention. Examples ofsuch monomers include acrylates and methacrylates such astrimethylolpropane trimethacrylate or trimethylolpropane triacrylate.The preferred compositions of the invention contain 0.001-5%, preferably0.005-4%, more preferably 0.01-3% by weight of a polyfunctional monomersuch as trimethylolpropane trimethacrylate ester or trimethylolpropanetriacrylate ester.

EXAMPLE 1 Chemical Resistance Test

To compare chemical resistance a topcoat formulation according to thepresent disclosure was compared against a commercial polish topcoatformulation and a commercial enhancement type topcoat formulation . Weemployed the conventional MEK double rub test except that acetonesubstituted for the methyl ethyl ketone. Thin films of each formulationwere prepared on glass microscope slides. Each film was formed to a 5mil wet thickness. The commercial enhancement type formulation and theformulation of the present disclosure were cured by exposure to UV lightusing a Brisa™ lamp. A very thin, unpolymerized tacky top layer waswiped to dryness using 99 wt % isopropanol. The polish formulation wasnot cured, but was dried under ambient conditions. All specimens wereaged under conditions of ambient light and temperature for 24 hours.Following aging, each sample was individually rubbed with cotton padssoaked in 99 wt % acetone. The polish formulation was completely removedby two rubs. The formulation of the present invention was dulled by tworubs, but remained intact for at least 150 rubs. The enhancementformulation remained shiny and intact for at least 200 rubs.

EXAMPLE 2 Pencil Hardness Test

To test scratch resistant, we recorded the lowest “H” number of thepencil which dented test samples prepared as given in Example 1. We alsorecorded the lowest “H” number of the pencil capable of tearing testfilms. The polish formulation was dented and torn by 3H and 4H pencils,respectively. The formula of the present disclosure was dented and tornrespectively by 3H and 6H pencils. The enhancement formula was dented bya 4H pencil and was not torn even by the hardest pencil (6H). This testshowed that the present disclosure had a significant better scratchresistance than the nail polish formula.

INDUSTRIAL UTILITY

This invention has industrial applicability in providing compositionsand methods for improving the adhesion of nail coatings to natural nailswithout requiring abrasion of the natural nail. The invention furtherprovides means for removing a nail coating without requiring abrasion ofthe natural nail surface or extended removal times soaking in a solvent.

1. A polymerizable composition comprising: at least one first reactive(meth)acrylate monomer; at least one second reactive (meth)acrylatemonomer; at least one reactive urethane (meth)acrylate; at least oneaddition-polymerizable, ethylenically-unsaturated monomer; at least onenon-reactive, solvent-dissolvable polymer; and at least one non-reactivesolvent; wherein upon exposure to a polymerization accelerant, saidpolymerizable composition cures to an acrylic thermoset having voidsdefined therein.
 2. The polymerizable composition according to claim 1,wherein said at least one first reactive (meth)acrylate monomer isselected from the group consisting of ethyl methacrylate (EMA),hydroxypropyl methacrylates (HPMA), pyromellitic dianhydride glyceryldimethacrylate, and mixtures thereof.
 3. The polymerizable compositionaccording to claim 2, wherein said at least one second reactive(meth)acrylate monomer or polymer selected from the group consisting of:hydroxyethylmethacrylate (HEMA), hydroxypropylmethacrylate (HPMA), ethylmethacrylate (EMA), tetrahydrofurfuryl methacrylate (THFMA),pyromellitic dianhydride di(meth)acrylate, pyromellitic dianhydrideglyceryl dimethacrylate, pyromellitic dimethacrylate, methacroyloxyethylmaleate, 2-hydroxyethyl methacrylate/succinate, 1,3-glyceroldimethacrylate/succinate adduct, phthalic acid monoethyl methacrylate,acetoacetoxy ethyl methacylate (AAEMA), and mixtures thereof.
 4. Thepolymerizable composition according to claim 3, further comprising atleast one compound selected from the group consisting of polypropyleneglycol monomethacrylates, polyethylene glycol monomethacrylates, andmixtures thereof.
 5. The polymerizable composition according to claim 1,wherein said polymerization accelerant is selected from the groupconsisting of thermal conduction and/or radiation, visible radiation, UVradiation, electron beam radiation, amines, peroxides, and combinationsthereof.
 6. The polymerizable composition of claim 1, wherein said atleast one non-reactive, solvent-dissolvable polymer is a celluloseester.
 7. The polymerizable composition of claim 6, wherein saidcellulose ester is a cellulose acetate alkylate.
 8. The polymerizablecomposition of claim 7, wherein said cellulose acetate alkylate isselected from the group consisting of cellulose acetate butyrate,cellulose acetate propionate, and mixtures thereof.
 9. The polymerizablecomposition of claim 1, wherein said at least one non-reactive,solvent-dissolvable polymer is present at from about 5 to about 70 wt %.10. The polymerizable composition of claim 1, wherein said at least onenon-reactive, solvent-dissolvable polymer is present at from about 10 toabout 60 wt %.
 11. (The polymerizable composition of claim 1, whereinsaid at least one non-reactive, solvent-dissolvable polymer is presentat from about 20 to about 50 wt %.
 12. The polymerizable compositionaccording to claim 1, further comprising an adhesion-promoting(meth)acrylate.
 13. The polymerizable composition according to claim 12,wherein said adhesion-promoting (meth)acrylate is selected from thegroup consisting of tetrahydrofurfural methacrylate, ethyl methacrylate,hydroxypropyl methacrylate, pyromellitic dianhydride glyceryldimethacrylate, and mixtures thereof.
 14. The polymerizable compositionaccording to claim 1, further comprising pyromellitic glyceryldimethacrylate.
 15. The polymerizable composition of claim 1, furthercomprising at least one colorant.
 16. The polymerizable composition ofclaim 1, further comprising at least one rheology agent.
 17. Thepolymerizable composition of claim 16, wherein said at least onerheology agent is a fumed silica.
 18. The polymerizable composition ofclaim 17, wherein a surface of said fumed silica is modified withpolydimethylsiloxane.
 19. The polymerizable composition of claim 17,wherein said at least one rheology agent is a polyamide.
 20. Thepolymerizable composition of claim 19, wherein said at least onerheology agent present at up to about 10 wt %.
 21. The polymerizablecomposition of claim 1, wherein said at least one at least one urethane(meth)acrylate has a molecular weight of from about 300 to about 1,000.22. The polymerizable composition of claim 1, wherein said at least onenon-reactive solvent is selected from the group consisting of ketones,alkyl acetates, alcohols, alkanes, alkenes, and mixtures thereof. 23.The polymerizable composition of claim 1, wherein said at least onenon-reactive solvent is selected from the group consisting of acetone,ethyl acetate, butyl acetate, isopropyl alcohol, ethanol, methyl ethylketone, toluene, hexane, and mixtures thereof.
 24. The polymerizablecomposition of claim 1, wherein said at least one non-reactive solventis acetone.
 25. The polymerizable composition of claim 1, wherein saidat least one non-reactive solvent is included at up to about 70 weightpercent.
 26. The polymerizable composition of claim 1, furthercomprising at least one photoinitiator.
 27. The polymerizablecomposition of claim 26, wherein said at least one photoinitiator isselected from the group consisting of benzoylphenylphosphinates,cyclohexylphenyl ketones, benzyl ketals, and mixtures thereof.
 28. Thepolymerizable composition of claim 3, wherein the at least one firstreactive (meth)acrylate is HPMA.
 29. The polymerizable composition ofclaim 3, wherein the at least one second reactive (meth)acrylate isHEMA.
 30. The polymerizable composition of claim 28, wherein the atleast one second reactive (meth)acrylate is HEMA.
 31. The polymerizablecomposition of claim 30, wherein the ethylenically unsaturated monomerhas the formula:

wherein R₁ is H, a C₁₋₃₀ straight or branched chain alkyl, aryl,aralkyl; R₂ is a pyrrolidone, or a substituted or unsubstitutedaromatic, alicyclic, or bicyclic ring where the substituents are C₁₋₃₀straight or branched chain alkyl, or COOM wherein M is H, a C₁₋₃₀straight or branched chain alkyl, pyrrolidone, or a substituted orunsubstituted aromatic, alicyclic, or bicyclic ring where thesubstituents are C₁₋₃₀ straight or branched chain alkyl which may besubstituted with one or more hydroxyl groups, or [(CH2)_(m)O]_(n)Hwherein m is 1-20, and n is 1-200.
 32. The polymerizable composition ofclaim 30, wherein the ethylenically unsaturated monomer is adifunctional monomer having the formula:

wherein R₃ and R₄ are each independently H, a C₁₋₃₀ straight or branchchain alkyl, aryl, or aralkyl; and X is [(CH2)_(x)O_(y)]_(z) wherein xis 1-20, and y is 1-20, and z is 1-100.
 33. The polymerizablecomposition of claim 30, wherein the ethylenically unsaturated monomeris selected from the group consisting of trifunctional acrylates,trifunctional methacrylates, polyfunctional acrylates and polyfunctionalmethacrylates.